JP2001020176A - Deodorization-processing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent stable deodorization-processing agent, capable of being supplied as a finely pulverized aqueous dispersion and generating less decomposition smell. SOLUTION: This deodorization-processing agent contains at least one selected from a dual complex oxide A consisting of titanium and silicon, a dual complex oxide B consisting of titanium and zirconium and a ternary complex oxide C consisting of titanium, silicon and zirconium, and also the specific surface area of the complex oxide is >=100 m2/g. It contains a deodorizing catalyst, a dispersant hardly oxidation decomposed by the irradiation of ultraviolet light and water, and the mean diameter of the deodorizing catalyst is 0.1-5 μm. As the dispersing agent, at least one kind of an inorganic dispersing agent selected from sodium hexametaphosphate, sodium tripolyphosphate, boric acid, sodium pyrophosphate, sodium metaborate, trisodium phosphate and their potassium salt is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a binary composite oxide composed of titanium and silicon, a binary composite oxide composed of titanium and zirconium, and / or titanium.
The present invention relates to a deodorizing agent containing a ternary composite oxide composed of silicon and zirconium. More specifically, the deodorant processing agent is an aqueous dispersion which is finely divided and has a stable dispersion state by using a specific inorganic dispersant which is less oxidatively decomposed by ultraviolet irradiation, and exhibits a function of decomposing odor components. It is a deodorizing agent that can be used especially for fiber processing.

[0002]

2. Description of the Related Art In recent years, as environmental issues have been taken up significantly, interest in not only controlling the emission of environmental malignant substances into society but also smells in daily life has been increasing. For example, Japanese Unexamined Patent Publication No. 5-55184 proposes a method for deodorizing by irradiation of ultraviolet light, such as titanium oxide exhibiting a photoexcited catalytic function of providing a positive deodorizing effect against malodor. Such techniques are applied to fiber fabrics, for example, interior materials such as clothing and curtains, sanitary materials, and filters for air purifiers. As a processing method, there is generally known a method in which a deodorant such as titanium oxide is directly dispersed and kneaded in a fiber-forming polymer and then spun when producing a chemical fiber or a synthetic fiber.

There is also a processing example in which titanium oxide is used in the form of an aqueous dispersion. However, when the dispersant or stabilizer used for forming a dispersion is mainly composed of an organic substance, it is photo-excited when irradiated with ultraviolet rays. The organic substance is oxidatively decomposed by the catalytic function, and the dispersed state becomes unstable, and sedimentation occurs, and the problem of odor often occurs.

[0004] Similarly, when processed into fiber cloth,
There has been a problem in that organic substances such as dispersants and stabilizers are oxidatively decomposed by the photoexcited catalytic function, thereby generating an odor.

[0005]

SUMMARY OF THE INVENTION In view of the background of the prior art, the present invention provides an excellent deodorant processing agent which can be supplied in a stable, finely divided aqueous dispersion and which generates little decomposition odor. It will not be provided.

[0006]

The present invention employs the following means to solve the above-mentioned problems. That is, the deodorizing agent of the present invention is a binary composite oxide A composed of titanium and silicon, a binary composite oxide B composed of titanium and zirconium, and titanium,
Ternary composite oxide C comprising silicon and zirconium
A deodorizing catalyst comprising a deodorizing catalyst by ultraviolet irradiation, a dispersant, and water, wherein the deodorizing catalyst comprises at least one member selected from the group consisting of: and a specific surface area of the composite oxide is 100 m ² / g or more. Has an average particle size of 0.01 to 5 μm, and the dispersant is sodium hexametaphosphate, sodium tripolyphosphate, boric acid, sodium pyrophosphate, sodium metaborate,
It is characterized by using at least one inorganic dispersant selected from trisodium phosphate and potassium salts thereof.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention has been made under the above-mentioned problems,
Stable, can be supplied in finely divided aqueous dispersion, and
We thoroughly studied excellent deodorant processing agents that generate little decomposition odor, and made a deodorant processing agent using a specific composite oxide and inorganic dispersant. Was determined.

That is, the present invention provides a binary composite oxide A comprising titanium and silicon which are deodorizing agents, a binary composite oxide B comprising titanium and zirconium, and titanium, silicon and zirconium. At least one selected from the ternary composite oxides C, natural fibers, synthetic fibers, various synthetic resin films and various synthetic resins,
Further, a means capable of processing various materials such as a composite material composed of a combination of the fiber, the film and the synthetic resin is employed.

The binary composite oxide A composed of titanium and silicon (hereinafter referred to as composite oxide A) and the binary composite oxide B composed of titanium and zirconium (hereinafter referred to as composite oxide B) used in the present invention. ) And / or a ternary composite oxide C comprising titanium, silicon and zirconium (hereinafter referred to as composite oxide C) is a mixed phase in which another phase is dissolved in a crystal phase, that is, a solid solution.

[0010] Binary composite oxides composed of titanium and silicon are known as solid acids, exhibit remarkable acidity not found in each of the constituent oxides, and have a high surface area.

That is, the binary composite oxide composed of titanium and silicon is not simply a mixture of titanium dioxide and silicon dioxide, but is formed by titanium and silicon forming a so-called binary composite oxide. It can be recognized that characteristics are exhibited.

The binary composite oxide B and the composite oxide C are also specified as composite oxides having the same properties as the composite oxide A. Furthermore, as a result of analysis by X-ray diffraction, the composite oxide has a fine structure that is amorphous or almost amorphous.

All of the composite oxides used in the present invention exhibit excellent odor component decomposition activity, particularly excellent activity at low temperatures. Although the mechanism is not certain, it is considered that the properties of the composite oxide have a favorable effect on the odor component decomposition activity.

It is preferable that each of the composite oxides A to C has a surface area of 100 m ² / g or more. This is because the deodorizing reaction is thought to be a process in which the odorous component is adsorbed on the support or the composite oxide (catalyst) and then undergoes ultraviolet oxidation decomposition. It is thought to have a significant effect. The larger the surface area, the better the adsorptivity is, and if it is less than 100 m ² / g, it is insufficient. The composition of the composite oxide (catalyst) is such that TiO ₂ is present in an amount of ₂₀ to 95 mol% in terms of oxide, and the remainder is Si.
A preferred result is a composition occupied by O ₂ , ZrO ₂ or SiO ₂ .

As the composite oxide used in the present invention, those produced by the method described in Japanese Patent Application Laid-Open No. 5-55184 can be used.

A dry pulverizer or a wet pulverizer can be used for dispersing the composite oxide in water and forming fine particles. In order to enhance the stability of the dispersion, the average particle size of the composite oxide is preferably from 0.01 to 5 μm, and more preferably from 0.01 to 1 μm.

The content of the composite oxide in the deodorizing agent of the present invention is practically preferably 3 to 70% by weight, more preferably 3 to 40% by weight. In addition, as the dispersion stabilizer, an inorganic dispersant that is unlikely to be decomposed by a photocatalytic reaction can be preferably used. As such an inorganic dispersant, at least one selected from sodium hexametaphosphate, sodium tripolyphosphate, boric acid, sodium pyrophosphate, sodium metaborate, trisodium phosphate and potassium salts thereof can be used. These inorganic dispersants can be used alone or in a combination of 0.03 to 10% by weight based on the binary composite oxide and the ternary composite oxide.

An organic dispersant may be used as long as the performance is not hindered. The deodorizing agent of the present invention thus obtained can further contain various functional agents such as an antibacterial agent, a flame retardant, a water repellent and an antistatic agent. However, it is necessary to check the dispersion stability of the deodorizing agent and the decomposability of various functional agents by the photocatalytic reaction.

[0019]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The percentages and parts in the examples are on a weight basis unless otherwise specified. The quality evaluation in the examples was performed according to the following method.

<Dispersion Stability of Processing Agent> 30 ml of the processing agent was placed in a 30-ml test tube with a stopper, and the stability of the dispersion state after standing at 30 ° C. and room temperature for one month was evaluated. ○: No change △: Slight sedimentation, reusable after stirring ×: Sedimentation separation, unusable

<Decomposition odor of processing agent> 100 ml of processing agent was placed in a 500 ml glass Erlenmeyer flask, sealed and left under an ultraviolet lamp (UV intensity 0.9 mW / cm ² ) for 24 hours. Sensory evaluation was performed. In addition, the sensory evaluation evaluated in six steps based on the following criteria, and described the average value of ten persons. 5: Strong smell 4: Strong smell 3: Easy to detect smell 2: Weak smell to know what smell 1: Almost no smell 0: No smell

<Evaluation of Deodorization Rate Using Detector Tube> A 500 cm glass Erlenmeyer flask was filled with a work cloth of 10 cm × 10 cm, and acetaldehyde gas was put therein so as to have an initial concentration of 100 ppm. 0.9 mW / cm ² ) After standing for 3 hours, the residual acetaldehyde gas concentration was measured with a gas detector tube. The deodorization rate was calculated by the following equation. Deodorization rate (%) = 100 × ([Initial concentration] − [Residual concentration after 3 hours]) / [Initial concentration] The deodorizing rate was also measured for ammonia gas and methyl mercaptan gas in the same manner.

<Odor evaluation of deodorant property against tobacco odor> 5
With the mouth of a 00 ml glass Erlenmeyer flask down, insert a 3 cm smoking cigarette into the mouth of the flask, place it for 20 seconds, quickly insert a 10 cm x 10 cm work cloth and seal with a glass stopper. After leaving under an ultraviolet lamp (UV intensity: 0.9 mW / cm ² ) for 3 hours, the glass stopper was opened, the work cloth was taken out, the residual odor of the flask was smelled, and the deodorizing property was evaluated organoleptically. Next, the taken-out work cloth was left under a fluorescent lamp for 1 hour, and then the smell of the work cloth was smelled. The sensory evaluation was performed in the same six-stage evaluation as the sensory evaluation of the decomposition odor of the processing agent.

<Evaluation of Odor of Decomposed Odor> A 500 cm glass Erlenmeyer flask was filled with a 10 cm × 10 cm work cloth.
Close the cap and place it under an ultraviolet lamp (UV intensity 0.9mW / cm
² ) The mixture was allowed to stand for 3 hours, then the stopper was opened and the odor in the flask was smelled, and the decomposition odor of the work cloth was evaluated organoleptically. The sensory evaluation was performed in the same six-stage evaluation as the sensory evaluation of the decomposition odor of the processing agent.

Example 1 A composite oxide A was used as a deodorant component using sodium hexametaphosphate as a dispersant. The composition ratio is Ti
This is a binary composite oxide composed of O ₂ : SiO ₂ = 4: 1 (molar ratio) and having a specific surface area of 195 m ² / g.

The average particle size of this dispersion is 0.22 μm
(Shimadzu Laser Diffraction Viscometer SALD
-2000 J). The addition amount of sodium hexametaphosphate (dispersant) in this dispersion was 5% by weight,
The added amount of the composite oxide A was 20% by weight. This dispersion was designated as deodorant A.

Table 1 shows the evaluation of the dispersion stability and the decomposition odor of the deodorizing agent A. As can be seen from Table 1, there was no problem.

Next, a polyester cloth having a basis weight of 180 g / m ² was immersed in a treatment liquid having the following composition, squeezed with a mangle (squeezing ratio: 80%), dried at 130 ° C. for 2 minutes, and dried at 180 ° C. with a pin tenter. Dry heat treatment was performed for 30 seconds to obtain a deodorized cloth A. Treatment liquid formulation (water dispersion) Deodorant A 10 g / l Silicone binder 15 g / l

Using the deodorized processed cloth A and the unprocessed cloth for comparison, the deodorization rate (acetaldehyde, ammonia, methyl mercaptan), the deodorant odor evaluation against cigarette odor, and the odor evaluation of decomposed odor using a detector tube were evaluated. The results are shown in Table 2.

As can be seen from Table 2, good results were obtained in both the deodorizing rate and the deodorizing property of the tobacco with respect to the untreated cloth, and the decomposition odor was equivalent to that of the untreated cloth and was at a satisfactory level.

Example 2 The same sodium hexametaphosphate as in Example 1 was used as a dispersant, and a composite oxide B was used as a deodorant component. The composition ratio of the composite oxide B was TiO ₂ : ZrO ₂ = 4: 1 (molar ratio), and the binary composite oxide having a specific surface area of 150 m ² / g was atomized and dispersed by a wet disperser.

The average particle size of this dispersion is 0.28 μm
(Shimadzu Laser Diffraction Viscometer SALD
-2000 J). The addition amount of sodium hexametaphosphate (dispersant) in this dispersion was 5%, and the addition amount of this composite oxide B was 20%. This dispersion was designated as deodorant agent B.

Table 1 shows the evaluation of dispersion stability and decomposition odor of the deodorant agent B. As can be seen from Table 1, there was no problem. Next, using the same polyester fabric as in Example 1, the same processing as in Example 1 was performed and evaluated. The results are shown in Table 2. As can be seen from Table 2, good results were obtained in both the deodorizing rate relative to the untreated cloth and the deodorizing property of the tobacco, and the decomposition odor was at the same level as that of the untreated cloth without any problem.

Example 3 The same sodium hexametaphosphate as in Example 1 was used as a dispersant, and the composite oxide C was used as a deodorant component. The composition ratio of this composite oxide C is TiO ₂ : SiO ₂ : ZrO ₂ = 8
0: 16: 4 (molar ratio), specific surface area 190 m
^The ternary composite oxide of ² / g was atomized and dispersed by a wet disperser.

The average particle size of this dispersion is 0.20 μm
(Shimadzu Laser Diffraction Viscometer SALD
-2000 J). The addition amount of sodium hexametaphosphate (dispersant) in this dispersion was 5%, and the addition amount of composite oxide C was 20%. This dispersion was designated as deodorant processing agent C.

Table 1 shows the evaluation of dispersion stability and decomposition odor of the deodorizing agent C. As can be seen from Table 1, there was no problem. Next, using the same polyester fabric as in Example 1, the same processing as in Example 1 was performed and evaluated. The results are shown in Table 2. As can be seen from Table 2, good results were obtained in both the deodorizing rate relative to the untreated cloth and the deodorizing property of the tobacco, and the decomposition odor was at the same level as that of the untreated cloth without any problem.

Example 4 The same complex oxide A as used in Example 1 was used as a deodorant component using sodium tripolyphosphate as a dispersant.
It was atomized and dispersed in a wet disperser.

The average particle size of this dispersion is 0.30 μm
(Shimadzu Laser Diffraction Viscometer SALD
-2000 J). The addition amount of sodium tripolyphosphate (dispersant) in this dispersion was 5%, and the addition amount of composite oxide A was 20%. This dispersion was designated as deodorant processing agent D.

Table 1 shows the evaluation of dispersion stability and decomposition odor of the deodorizing agent D. As can be seen from Table 1, there was no problem. Next, using the same polyester fabric as in Example 1, the same processing as in Example 1 was performed and evaluated. The results are shown in Table 2. As can be seen from Table 2, good results were obtained in both the deodorizing rate relative to the untreated cloth and the deodorizing property of the tobacco, and the decomposition odor was at the same level as that of the untreated cloth without any problem.

Comparative Example 1 A binary composite oxide A used in Examples 1 and 4 was used as a deodorant component using a polyoxyethylene nonylphenyl ether-based organic surfactant as a dispersant, and this was subjected to a wet dispersing machine. Fine particles were dispersed. The average particle size of this dispersion was 0.52 μm (measured with a laser diffraction type viscosity distribution meter SALD-2000J manufactured by Shimadzu Corporation). The addition amount of the polyoxyethylene nonylphenyl ether surfactant (dispersant) in this dispersion was 5%, and the addition amount of the composite oxide A was 20%. This dispersion was designated as deodorant E.

Table 1 shows the evaluation of dispersion stability and decomposition odor of the deodorizing agent E. As can be seen from Table 1, the decomposition odor was strong and the dispersion stability was poor.

Next, using the same polyester fabric as in Example 1, the same processing as in Example 1 was carried out and evaluated. The results are shown in Table 2. As can be seen from Table 2, slightly better results were obtained in both the deodorization rate relative to the raw cloth and the deodorizing property of the tobacco.
Decomposition odor was a problem at a level where the odor was considerably stronger than that of the untreated cloth and Examples 1-4.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

According to the present invention, a deodorizing agent which is an aqueous dispersion having a stable dispersion state and exhibits an excellent deodorizing function (decomposes odor components) which is less likely to decompose organic substances even when used. In particular, a material suitable for fiber processing can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshihiko Ito 1-1-1, Sonoyama, Otsu-shi, Shiga Prefecture Toray Industries, Inc. Shiga Plant (72) Inventor Koichi Saito 1-1-1, Sonoyama, Otsu-shi, Shiga No. 72 Toray Industries, Inc. Shiga Plant (72) Inventor Noriyuki Yamauchi 1 Kyoto Nishinokyo Uchihata-cho, Nakagyo-ku, Kyoto (72) Inventor Katsuo Sasatsu 1 Nishi-no-Kyochihata-cho, Nakagyo-ku, Kyoto Daikyo Chemical Co., Ltd. F term in the company (reference) 4L031 BA09 BA12 BA13 BA38 CA08 CB09 DA13

Claims (3)

[Claims] 1. A binary composite oxide A comprising titanium and silicon, a binary composite oxide B comprising titanium and zirconium, and a ternary composite oxide C comprising titanium, silicon and zirconium. At least one
The composite oxide has a specific surface area of 1
It contains a deodorant catalyst, a dispersant, and water by ultraviolet irradiation of not less than 00 m ² / g, and has an average particle diameter of 0.0
1 to 5 μm, wherein the dispersant is at least one inorganic dispersant selected from sodium hexametaphosphate, sodium tripolyphosphate, boric acid, sodium pyrophosphate, sodium metaborate, trisodium phosphate and potassium salts thereof. A deodorizing agent characterized by being used. 2. The method according to claim 1, wherein the complex oxide is contained in the deodorizing agent in an amount of 3 to 7%.
0% by weight, and the dispersant is contained in the deodorizing agent in an amount of 0.0
The deodorizing agent according to claim 1, which is contained in an amount of 3 to 10% by weight. 3. The deodorizing agent according to claim 1, wherein the deodorizing agent is used for fiber processing.